Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C13H9N2O)Cl]2·(CH3CN)2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu(C13H9N2O)Cl]2·(CH3CN)2 (C30H24Cl2Cu2N6O2),has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1-, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) (A), α = 81.338(3),β= 88.173(4), γ = 66.199(3)°, V = 718.9(2) (A)3, Z = 1, Mr = 698.53, F(000) = 354, Dc = 1.613 g/cm3,μ(MoKα) = 1.705 mm-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones (I＞ 2σ(Ⅰ)). In the title complex, each copper(Ⅱ) atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms (one nitrogen atom, two oxygen anions,and one chlorine atom). Two copper(Ⅱ) atoms are bridged by two oxygen anions (O(1) and O(1a)) of two phenolates to form a Cu(Ⅱ)-Cu(Ⅱ) binuclear entity, and the distance between two copper(Ⅱ)atoms is 3.0144(15) (A).     

Synthesis of novel nitrogen‐ and sulfur‐containing conjugated polymers used as hole‐transporting materials for organic light‐emitting diodes

Two series of highly soluble novel nitrogen‐ and sulfur‐containing conjugated polymers were synthesized via an acid‐induced self‐polycondensation of functional monomers with methyl sulfinyl and aromatic groups. The well‐defined structures of synthesized polymers were confirmed by their NMR and IR spectra. The highest occupied molecular orbital energy values for these materials, estimated by cyclic voltammetry, showed a broad range of values from about 5.0 to 5.2 eV used as hole‐transport layers (HTL) in two‐layer light‐emitting diodes ITO/HTL/Alq₃/Mg:Ag [ITO = indium tin oxide, and Alq₃ = tris(8‐quinolinato) aluminum]. The typical turn‐on voltage of these diodes was about 4–5 V. The maximum brightness of the device was about 3440 cd/m² at 20 V. The maximum efficiency was estimated to be 0.15 lm/W at 10 V. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1321–1333, 2002     

Nitrogen speciation of polar petroleum compounds by compound class separation and on-line liquid chromatography – mass spectrometry (LC-MS)

Chromatography on Attapulgus clay and on silicic acid has been used to isolate ‘neutral’ and ‘basic’ nitrogen fractions from the 650–1050 °F distillate of an off-shore Californian crude oil. These polar compounds were subjected to on-line liquid chromatography – mass spectrometric (LC-MS) analysis using low voltage electron-impact ionization high resolution mass spectrometry (LVEI HRMS) and deuterated ammonia chemical ionization (ND₃ Cl) to determine the molecules' elemental composition and number of exchangeable hydrogen atoms. On-line separation of heavy oils into saturated, 1–4 ring aromatic, and polar compounds was performed by normal phase high performance liquid chromatography (HPLC) on a dinitroanilinopropyl (DNAP) silica column.     

Fluorescent response of sol-gel derived ormosils for optical ammonia sensing film

Optical sensing films for ammonia have been investigated based on a fluorescent indicator aminofluorescein (AF). AF was immobilized in diverse organically modified silicates (ORMOSILSs) obtained by copolymerizing various proportions of methyltrimethoxysilane (Me-TriMOS), phenyltrimethoxysilane (Ph-TriMOS), dimethyldimethoxysilane (DiMe-DiMOS), and diphenyldimethoxysilane (DiPh-DiMOS) with tetramethoxysilane (TMOS). The effective polarities of ormosils were probed by using the solvatochromic dye E_T (30) [2,6-diphenyl-4-(2,4,6-triphenyl-N-pyridino)]phenolate. Compared with the fluorescent responses of fluorescein and fluorescein isothiocyanate, the fluorescent intensity enhancement of AF for ammonia was caused by the reaction between ammonia and the NH₂ group on AF. The reaction may cause the reduction of the intermolecular self-quenching of AF to make a fluorescence enhancement of sensing film in NH₃ solution. The ammonia sensing range and rate of response were found to highly depend on the type and content of organosilicon precursors employed. Films prepared with a 1:3, 1:1.5, 1:1.2, or 1:1 mole ratio (TMOS:Me-TriMOS, TMOS:Ph-TriMOS, TMOS:DiMe-DiMOS, or TMOS:DiPh-DiMOS) was found to be the best in terms of stability and response. Their detection limits for ammonia in water was 0.01, 0.5, 0.2, and 0.5 μg ml⁻¹, respectively.     

SYNTHESIS OF NEW AROMATIC POLY（AMIDE IMIDE）S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (T8) are in the range of 301-327℃, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521℃.     

Absolute Calibration of TALIF of Atomic Nitrogen by NO Titration—Experimental and Theoretical Analysis

The method of absolute calibration of the TALIF signal of atomic nitrogen by NO titration in the afterglow of a flow tube reactor has been analyzed using TALIF and emission spectroscopy. An increase in production of atomic nitrogen at titration beginning and an asymmetric parabolic curve for emission of NObands have been observed. Of three possible explanations of these effects the model of wall recombination was favored: it led to fitted wall recombination coefficients referring to wall loss factors, which where in the same dimension as literature values and was able to simulate a hysteresis effect, which has been observed experimentally. According to the observations the titration end point cannot be used to determine the atomic nitrogen density in the afterglow before any NO has been added into the system as the titer produces part of this density itself. But for absolute calibration purposes referring to the wall recombination model the linear decrease of the TALIF signal with increasing titer concentration can still be used as straight line of calibration. Only a correction of the calibration factor by a factor of 0.59 for 5 mbar titrations has to be taken into account as the titer shows wall interaction not only in a catalytic way, but is partly consumed.     

Ammonium hydroxide detoxification of spruce acid hydrolysates

When dilute-acid hydrolysates from spruce are fermented to produce ethanol, detoxification is required to make the hydrolysates fermentable at reasonable rates. Treatment with alkali, usually by overliming, is one of the most efficient approaches. Several nutrients, such as ammonium and phosphate, are added to the hydrolysates prior to fermentation. We investigated the use of NH₄OH for simultaneous detoxification and addition of nitrogen source. Treatment with NH₄OH compared favorably with Ca(OH)₂, Mg(OH)₂, Ba(OH)₂, and NaOH to improve fermentability using Saccharomyces cerevisiae. Analysis of monosaccharides, furan aldehydes, phenols, and aliphatic acids was performed after the different treatments. The NH₄OH treatments, performed at pH 10.0, resulted in a substantial decrease in the concentrations of furfural and hydroxymethylfurfural. Under the conditions studied, NH₄OH treatments gave better results than Ca(OH)₂ treatments. The addition of an extra nitrogen source in the form of NH₄Cl at pH 5.5 did not result in any improvement in fermentability that was comparable to NH₄OH treatments at alkaline conditions. The addition of CaCl₂ or NH₄Cl at pH 5.5 after treatment with NH₄OH or Ca(OH)₂ resulted in poorer fermentability, and the negative effects were attributed to salt stress. The results strongly suggest that the highly positive effects of NH₄OH treatments are owing to chemical conversions rather than stimulation of the yeast cells by ammonium ions during the fermentation.     

π-facial interactions between Cl and [S4N3]. X-ray crystal structure of [S4N3]Cl

The X-ray structure of [S₄N₃]Cl reveals three independent molecules, which all display π-facial interactions between the Cl⁻ and the pseudo-aromatic [S₄N₃]⁺ rings to produce a structure containing “inverse sandwich” systems.     

Spectroscopic tests of a 2.3 μm tunable diode laser

A 2.3 μm near-room temperature tunable diode laser was tested for applications in high-resolution laboratory spectroscopy. It was mounted using a simple adaptor in a spectrometer usually used with lead-salt diode lasers, and was found to be electrically and optically compatible with the system. Good output power (several milliwatts) was observed, and a tuning range of 4460–4150 cm⁻¹ was achieved for laser temperatures of 210–310 K. Some spectra of N₂O and NH₃ were recorded in the 4300–4430 cm⁻¹ region. However, the laser was not generally useful due to noisy and unstable output and high sensitivity to optical feedback.     

杯芳烃与NO2硝化反应的研究

系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n＝4, 6, 8)与NO₂气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO₂的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨.